Molecular memory device

ABSTRACT

A novel memory cell is provided with an active region including a molecular system and ionic complexes distributed in the molecular system. A pair of write electrodes are arranged for writing information to the memory cell. The active region is responsive to an electric field applied between the pair of write electrodes for switching between an on state and an off state. The active region has a high impedance in the off state and a low impedance in the on state. A pair of read electrodes is used to detect whether the active region is in the on state or in the off state to read the information from the memory cell. Read electrodes may be made of different materials having different work functions to reduce leakage current.

CROSS REFERENCE

This application is a continuation of copending U.S. application Ser. No. 10/139,747, filed May 7, 2002, entitled MOLECULAR MEMORY DEVICE, which claims the benefit of U.S. Provisional Patent Application Ser. No. 60/289,056, filed on May 7, 2001, entitled ELECTRICALLY ADDRESSABLE MEMORY SWITCH WITH BUILT-IN LEAKAGE CURRENT BARRIER. The aforementioned applications are incorporated herein by reference.

FIELD OF THE INVENTION

The invention relates to a memory device, and more particularly to a memory device including a molecular system with ionic complexes distributed in the system.

BACKGROUND OF THE INVENTION

Various types of electrically addressable memory devices for computer data storage are known in the art. Most of these devices store a data bit as a charge in a capacitor. The charge state can be read out and the output signal used to control processes in a computer processor. Most of these devices require complex silicon processing steps and a dedicated device architecture which depends on memory type.

Memory devices are distinguished by their speed and data retention characteristic. Dynamic random access memory (DRAM) is a volatile memory characterized by a destructive read. This means that it is necessary to supply voltage to the memory bits at all times, or the information will disappear. Furthermore, each memory element has associated with it a transistor. Static random access memory (SRAM) stores data in a bistable flip-flop, commonly consisting of cross-coupled inverters. It is called “static” because it will retain a value as long as power is supplied. It is still volatile, i.e. it will lose its contents when the power is switched off, in contrast to ROM. SRAM is usually faster than DRAM, but each bit requires several transistors (about six), so that a lesser number of bits of SRAM fit in the same area as compared to DRAM.

Erasable programmable read only memory (EPROM) is a type of storage device in which the data is determined by electrical charge stored in an isolated (“floating”) MOS transistor gate. The isolation is good enough to retain the charge almost indefinitely (more than ten years) without an external power supply. The EPROM is programmed by “injecting” charge into the floating gate, using a technique based on the tunnel effect. This requires higher voltage than in normal operation (usually 12V-25V). The floating gate can be discharged through UV-illumination or electrically (EEPROM). Usually bytes or words can be erased and reprogrammed individually during system operation. EEPROM is more expensive and less dense than RAM. It is appropriate for storing small amounts of data which is changed infrequently. Another known non-volatile memory device is a ferromagnetic RAM (Fe-RAM), wherein the individual storage cells do not require a dedicated transistor.

When using passive memory devices connected in parallel, e.g., in form of an array, leakage current problems can occur. Leakage problems can be reduced, for example, by forming a Schottky barrier between an organometallic charge-transfer complex, such as M(TCNQ) and the underlying electrode. Alternatively, it has been proposed to provide a rectifying diode in series with the switching resistance at each intersection point of a memory array. This requires additional layers and processing steps.

The molecular composite material can have stable and metastable states that affect the retention time of the device. The device has an electrically insulating off state and at least one electrically conducting on state. The device can be switched reproducibly between the on state(s) and the off state by applying an electrical field across the device with a predetermined polarity and magnitude for a predetermined time.

It would therefore be desirable to provide a device that has a built-in barrier that reduces leakage currents.

SUMMARY OF THE INVENTION

The present invention provides a novel memory cell comprising an active region including a molecular system. Ionic complexes may be distributed in the molecular system. At least one write electrode applies an electric field to the active region to write information to the active region, and at least one read electrode is provided for reading the information from the active region.

In accordance with an aspect of the invention, the memory cell may includes a pair of write electrodes for writing information to the memory cell, and the active region responsive to an electric field applied between the first and second write electrodes for switching between an on state and an off state. A pair of read electrodes detect whether the active region is in the on state or in the off state to read the information from the memory cell.

In accordance with another aspect of the invention, a memory device includes a memory cell array composed of multiple memory cells arranged in row and column directions. Each memory cell comprises an active region including a molecular system and ionic complexes distributed in the molecular system, first and second write electrodes for applying an electric field to the active region, to write information to the memory cell, and first and second read electrodes for detecting electrical conductivity of the active region, to read the information from the memory cell.

In accordance with another aspect of the invention, a memory cell in a memory device including a memory cell array composed of multiple memory cells arranged in row and column directions, comprises first and second barrier elements arranged in contact with the active region to reduce leakage current.

In accordance with an embodiment of the invention, the first barrier element may be made of material having a work function different from a work function of the second barrier element. For example, the first and second barrier elements may be made of different metals.

Different materials having different work functions may be used for the read electrodes causing the resistance of a memory cell to be substantially different in a forward biased and reverse biased readout configuration. The write operation on the other hand, is unaffected by the difference in the work function of the readout electrodes.

Further features and advantages of the present invention will be apparent from the following description of preferred embodiments.

BRIEF DESCRIPTION OF THE DRAWINGS

The following figures depict certain illustrative embodiments of the invention. These depicted embodiments are to be understood as illustrative of the invention and not as limiting in any way.

FIGS. 1 a-1 d show a simplified structure of a molecular composite memory cell in various operational states;

FIG. 2 shows an exemplary four-terminal device in an on state according to an embodiment of the present invention;

FIG. 3 shows an array of memory cells, with an exemplary leakage current path indicated: and

FIG. 4 shows a schematic band diagram of a composite material with two different work function contact metals according to an embodiment of the present invention.

DETAILED DESCRIPTION OF CERTAIN ILLUSTRATED EMBODIMENTS

The present invention addresses and solves problems related to providing a novel memory device. The present invention overcomes these problems in part, by the provision of write and read electrodes adjacent an active region made of a molecular ensemble that exhibits a reproducible switching and memory effect applicable in macroscopic devices. The material of the active region is a composite material system that exhibits structural electronic instability in one dimension and enables static and dynamic control over the conductivity of such molecular systems. The mechanism for the memory and switching effect of these cells appears to be related to the structural electronic instability of one-dimensional molecular systems and associated with the dissociation of molecules and/or displacement of atoms in an external electrical field.

The development of molecular electronics stimulated the more detailed research of electrophysical characteristics of thin molecular films which offer new physical effects that may result in new technologies for electrical switching and memory applications. Although first reported in the 1960's, a generally accepted interpretation of such phenomena is still lacking. This is partly due to the non-reproducibility of the results, even when using identical compounds.

A number of different materials may be used as the molecular composite material. Exemplary materials are described below, but are also discussed in an article by Yu H. Krieger. entitled, “Structural Instability of One-Dimensional Systems As A Physical Principle Underlying The Functioning of Molecular Electronic Devices”. Journal of Structural Chemistry, Vol. 40, No. 4, 1999 (Yu H. Krieger), expressly incorporated by reference herein.

Many molecular memory cells can be made of a one-dimensional conductive molecular systems exhibiting structural instability. (Peierls-effect). These tend to have an S-shaped (reentrant) voltage-current characteristic with memory. The impedance of such memory cells can be between ˜10 MΩ and ˜100Ω, depending on the switching condition.

There are two predominant types of structural organization of such systems. First, these are strands of linear conjugated polymers, which are weakly bonded to each other and whose mutual arrangement is generally poorly organized. Second, these are crystal structures, where the individual molecules form one-dimensional columns and interact with each other much more actively than molecules from different columns do. Recently, molecular systems of both types were synthesized.

Polyconjugated systems primarily involve polyvinylenes. i.e., polymers with an acyclic conjugation system, in which the one-dimensional character of structure is dictated by the mechanism of conjugation in linear macromolecules. Polyacetylene is a classical representative of this class of polymers. Its electronic structure is a prototype for many other conjugated polymers.

Another wide class of molecular compounds formed from aromatic and heterocyclic molecules which possess high electric conductivity due to π-bonds between molecules. Such molecular systems are called π-complexes or charge transfer complexes, with those systems whose structure involves isolated one-dimensional columns or strands possessing pronounced electro-physical properties of interest for switching an memory applications. Molecular charge transfer complexes are donor-acceptor systems formed from two molecules: one possessing donor and another acceptor properties. Among the well-defined complexes with a one-dimensional structure, tetra-cyano-quino-dimethane (TCNQ) are planar molecules with unsaturated bonds, arranged in a crystal as parallel stacks forming a quasi-one-dimensional system.

In another class of one-dimensional systems, the cations are dynamically disordered. It involves molecular compounds having the general formula (TMTSF)₂X. Transition metal salts of K₂ Pt(CN)₄ Br₀₃×3H₂O (KCP) type are also the typical representatives of mixed-valence quasi-one-dimensional complexes, as are phthalocyanines and porphyrins. Moreover, pure inorganic compounds. such as NbSc₃, are also interesting examples of compounds with quasi-one-dimensional structure.

An exemplary molecular composite that forms part of a simplified molecular memory cell (MC) is shown in FIGS. 1 a-1 d. The molecular composite includes a quasi-one-dimensional—or at least structurally and electrically anisotropic—molecular matrix, wherein ionic complexes are distributed in the matrix. Polyconjugated compounds, such as the exemplary quasi-one-dimensional systems described above, for example, polyphenylacetylene, can be used as the anisotropic molecular matrix. The ionic complex can be a salt, such as sodium chloride (NaCl), cesium chloride (CsCl), or any other material that can dissociate in an applied electric field. The exemplary anisotropic molecular matrix is depicted in FIGS. 1 a-1 d as consisting of an assembly of chain-like molecules oriented perpendicular to the electrode surfaces. However, other orientations of those molecules or of anisotropic “channels” are possible as long as a charge separation of the type depicted in FIGS. 1 a-1 d is enabled.

While not being bound by theory, the following is currently believed by the inventors to describe the mechanism for the conductivity change of the molecular composite material. Electric switching in the molecular thin films depicted in FIGS. 1 a-1 d is characterized by the existence of two stable states, a high impedance state (off state) and a low impedance state (on state). The impedance of this off state is usually more than ˜10 MΩ. Switching from the to the on state occurs when an applied electric field exceeds a threshold value. The impedance of this on state is less than ˜100Ω. A transition from on state back to the off state takes place when the polarity of the electric field is reversed.

Two modes of the memory cell operation can be identified: the metastable mode (FIG. 1 b) and stable mode (FIG. 1 c). The stable mode of the memory cell operation may be characterized by a high threshold voltage level for switching between the off state and the on state (in the range of about 3-10V), low impedance of the on state (less than 100Ω), long switching time (1 ms and more) and long storage time (more than two month). Some memory cells exhibit substantially unchanged electrical properties after storage for six years.

Conversely, the metastable mode of the memory cell function is characterized by a low threshold voltage level for switching between the off state and the on state (in the range of about 0.1-0.5V), high impedance of the on state (wide region, about 1 kΩ-1MΩ), short switching time (less than 1 μs), and short storage time (between about 10 s and several hours).

FIG. 1 a illustrates the off state, where the electrical conductivity is essentially zero, assuming that the anisotropic molecular matrix itself is a good electrical insulator. When an external electric field E is applied, as indicated in FIG. 1 b, the sodium salt dissociates into sodium and chlorine ions, and the ions are displaced from their original position in the anisotropic molecular matrix, resulting in an increase in the electrical conductivity of the MC (on state) to the metastable state. Upon further increase of the electric field, the ions become more strongly separated (FIG. 1 c), accompanied by a still further increase in the conductivity of the MC, which attains the above-described stable state. When a very large field is applied over a long time, the anions and cations accumulate at the electrodes (FIG. 1 d), resulting in a sharp decrease in the electrical conductivity of the MC due to the absence of mobile charges (“off” state).

Referring now to FIG. 2, a four-terminal memory cell 20 according to an embodiment of the present invention includes an upper write electrode A, an upper read electrode B insulated from the upper write electrode A by an insulator 1, a lower read electrode C, a lower write electrode D, an insulator 2 disposed of between the lower read electrode C and the lower write electrode D for insulation purposes, and an active layer 22 made of composite material described above with reference to FIG. 1. For example, the active layer 22 may be provided in contact with each of the lower and upper read electrodes B and C.

When an electric field is applied between the write electrodes A and D, the ionic NaCl complex dissociates into Na⁺ and Cl⁻ ions. If the potential at the electrode A is positive with respect to the potential at the electrode D, the negatively charged Cl⁻ ions migrate towards the positive write electrode A, whereas the positively charged Na⁺ ions migrate towards the negative write electrode D. For example, to provide a writing operation, the write electrode A may be grounded, whereas a negative potential, e.g. −10 V, may be applied to the electrode D.

The read electrodes B and C as well as the insulators 1 and 2 prevent the ions from actually reaching the write electrodes A and B, which only provide the electric field. As a result, as discussed above with reference to FIG. 1, the electrical conductivity of the composite material layer 22 increases so that electric current can pass between the read electrode B and the read electrode C. This state corresponds to the on state of the device 40.

An erasing operation may be provided by applying between the write electrode A and the write electrode D an electric field having polarity opposite with respect to the polarity of the electric field applied to provide the writing operation. During the erasing operation, the device 40 is switched from its conducting state (on state) to its non-conducting state (“off” state). For example, to provide the erasing operation, the write electrode A may be grounded, whereas a positive potential, e.g. +10 V, may be supplied to the write electrode D.

A reading operation may be provided by measuring the impedance of the active layer 22 between the read electrodes B and C. To support the reading operation, the electrode B may be grounded, and a small negative potential, e.g. −0.1 V may be supplied to the electrode C.

The device 20 may be a four-terminal memory cell of a memory device including a memory cell array composed of multiple memory cells arranged in row and column directions, wherein the electrodes A and B can form, for example, the row electrodes of the memory cell array, and the electrodes C and D can form the column electrodes of the memory cell array.

FIG. 3 schematically illustrates the memory cell array of the present invention. When a particular memory cell of the memory cell array located, for example in the fifth row (R5) and the second column (C2) is read out, then a leakage current can also flow by a large number of cells. FIG. 3 illustrates an exemplary path for the leakage current via cells arranged at nodes [R5,C4], [R3,C4], and [R3,C2] of the memory cell array, where R and C respectively identify the row and column addresses of a particular node. Since many such paths are available, only a small cell resistance in the reverse direction can make it impossible to reliably read out the information stored, for example, in the cell arranged at node [R5,C2].

Referring to FIG. 4, the cell resistance can be increased substantially in the reverse direction by providing contacts to the composite layer 22 using barrier elements 42 and 44 made of different materials, such as Metal I and Metal II with different work functions WI and WII, respectively. The conduction band and valence band quasi-Fermi levels of the composite material are indicated in FIG. 4. It is clearly seen that electronic carriers, e.g., electrons, passing through the active layer 22 from Metal II into Metal I have to overcome a substantially larger potential barrier that electrons moving in the opposite direction. Suitable metals for a low work function Metal I are, for example, Al, Mg, Ag and In, whereas suitable metals or materials for a high work function Metal II are, for example, Au and Indium-Tin-Oxide (ITO). It is therefore possible to design memory cells with low leakage currents using the composite material disclosed herein.

The barrier elements 42 and 44 made of different materials having different work functions may be used as read electrodes for reading information from a memory cell by detecting impedance of the active layer 22 between the elements 42 and 44. The barrier elements having different work functions cause the impedance of the memory cell to be substantially different in a forward biased and reverse biased readout configuration. The writing operation, on the other hand is unaffected by the difference in the work function of the readout electrodes.

While the invention has been disclosed in connection with the preferred embodiments shown and described in detail, various modifications and improvements thereon will become readily apparent to those skilled in the art. 

1-18. (canceled)
 19. A method of assembling a memory device, comprising the steps of: forming an array of transistors; covering the transistors with a dielectric layer; forming conductive contacts to the transistors through the dielectric layer; forming memory elements with multiple selectable resistance values on the conductive contacts by self-assembly; and forming a common electrode On the memory elements connecting to each of the memory elements.
 20. The method of claim 19, wherein the step of forming memory elements includes depositing a first material that adheres only to the conductive contacts and not to the dielectric layer.
 21. The method of claim 20, wherein the first material is a polycojugated polymer.
 22. The method of claim 21, wherein the polyconjugated polymer is one of polyparaphenylene, polyphenylvinylene, polyaniline, polythiophene or polypyrrole.
 23. The method of claim 20, wherein the first material is a polymeric phtalocyanine.
 24. The method of claim 20, wherein the first material is a polymeric porphyrin.
 25. The method of claim 19, wherein the step of forming conductive contacts includes forming a conductive plug with a bottom contacting a transistor and a top, forming a barrier layer on the top of the conductive plug, and forming an adhesion layer on the barrier layer.
 26. The method of claim 25, wherein the step of forming memory elements includes locating the memory device within an enclosed chamber with a liquid monomer.
 27. The method of claim 26, wherein the step of forming memory elements further includes locating the memory device within an enclosed chamber with a monomer gas.
 28. The method of claim 27, wherein the liquid monomer and the monomer gas are methylphenylacetylen, and a polyconjugated polymer of polymethylphenylacetylene is formed as the memory elements.
 29. The method of claim 28, wherein the liquid monomer and the monomer gas are tetracyanobenzene, and cupperphtalocyanine is formed as the memory element.
 30. A method of forming a memory cell comprising: forming a first electrode; forming a memory element on the first electrode by self-assembly, wherein the memory element comprises a polymer that forms only on the first electrode and having multiple resistance values that are selectable by exposure of the polymer to an electric field; and forming a second electrode on the memory element
 31. The method of claim 30, wherein the polymer is polyconjugated polymer.
 32. The method of claim 31, wherein the polyconjugated polymer is one of: polyparaphenylene, polyphenylvinylene, polyaniline, polythiophene or polypyrrole.
 33. The method of claim 30, wherein the polymer is a polymeric phtalocyanine.
 34. The method of claim 30, wherein the phtalocyanine is cupperphtalocyanine.
 35. The method of claim 30, wherein the polymer is a polymeric porphyrin.
 36. A method for constructing a memory device, comprising: forming an array of transistors on a substrate; depositing a dielectric layer on the transistor array, forming contacts to the transistors through the dielectric layer; forming memory elements on the conductive contacts by self-assembly; and forming a common electrode on the memory elements.
 37. The method of claim 36, the memory elements have multiple selectable resistance values that can be selected via application of an electric field.
 38. The method of claim 36, firmer comprising forming a conductive plug on at least one of the conductive contacts, the conductive plug is exposed at a top surface of the dielectric layer.
 39. The method of claim 38, further comprising recessing the dielectric layer around the exposed portion of the conductive plug.
 40. The method of claim 38, further comprising forming a barrier layer on the exposed conductive plug.
 41. The method of claim 40, the barrier layer comprises tungsten.
 42. The method of claim 40, further comprising forming an adhesive layer on the barrier layer.
 43. The method of claim 42, the adhesive layer comprises at least one of copper and a copper alloy.
 44. The method of claim 42, further comprising forming a memory element on the adhesive layer, the memory element adheres only to the adhesive layer and not to the adjacent dielectric layer. 